||The corrosion mechanisms by liquid aluminum of three industrial materials have been studied: unalloyed steel (UAS), and ferritic and modified pearlitic cast irons (FCI and PCI, respectively). The behavior of these materials when in contact with liquid aluminum is different. Aluminum diffuses deep into the UAS and forms intermetallic compounds with iron at the surface and in the steel matrix. At the surface, only Fe2Al5 and FeAl3 are found. In the matrix, FeAl2 also is formed in agreement with the equilibrium Fe-Al diagram. From the matrix to FeAl2, the Al content in the ferrite increases progressively until Al saturation is reached. At this step, black elongated precipitates (Al4C3 and/or graphite) appear. Graphite lamellas present in both FCI and PCI constitute an efficient barrier to the Al diffusion. The high silicon content of the FCI leads to the formation of a phase free from Al and saturated in Si. For the PCI, a thin layer rich in Al and Si, which is formed between the matrix and Fe2Al5, limits the diffusion of atoms. The effects of Cr and P added in the PCI also are discussed.